Substituted indans

ABSTRACT

LUBRICANT COMPOSITIONS ARE PROVIDED COMPRISING A SUBSTITUTED INDAN HAVING THE STRUCTURE:   1,1,3-TRI(CH3-),3-(R-PHENYL),R-INDAN   IN WHICH R IS AT LAST ONE MEMBER OF THE GROUP CONSISTING OF HYDROGEN, ALKYL, PHENYL, CARBOXY ALKYL, CARBOXY PHENYL, PHENOXY AND THEIR THIOSUBSTITUTED DERIVATIVES. THE METHOD FOR THE PREPARATION OF THESE SUBSTITUTED INDANS IS ALSO PROVIDED.

United States Patent Oflice 3,792,096

Patented Feb. 12, 1974 vided which are thermally and oxidatively stablehaving 3,792,096 the structure: SUBSTITUTED INDANS Robert M. Gemmill,(in, Woodbury, and John w. Schick, f

Cherry Hill, N.J., assignors to Mobil Oil Corporation CH3 N Drawing.Original application June 24, 1969, Ser. No. 5 R

836,161, now Patent No. 3,640,870. Divided and this application Mar. 18,1971, Ser. No. 125,853

Int. Cl. C07c 41/00, 43/20 CH US. Cl. 260-612 R 2 Claims ABSTRACT OF THEDISCLOSURE Lubricant compositions are provided comprising a substitutedindan having the structure:

in which R is at least one member of the group consisting of hydrogen,alkyl, phenyl, carboxy alkyl, carboxy phenyl, phenoxy and theirthiosubstituted derivatives. B These substituted indans, as more fullyhereinafter described, have been found to be markedly etiec-tive notonly in possessing thermal and oxidative stability as lubri- CHS cants,per se, but also in imparting, as a blending stock, thermal andoxidative stability to lubricant compositions in the form of lubricantoils, greases and any of the aforementioned organic media such asautomatic trans- R mission fluids, hydraulic fluids, heat-exchangefluids and the like. In Which R 15 at least one member of the groupconsisting The organic compositions, of more specific importance, ofhydrogen, y phanyl, carboxv alkyl, carbcxy which are improved byblending with the substituted in- P y s P Y and their thiosubstimtedderivatives dans of the present invention may include mineral oils Tmethod for t Preparation of these substituted and synthetic oils'oflubricating viscosities. Of particular moans ls alsoptoyldedsignificance is the improvement of petroleum distillatelubricating oils having boiling points as high as 650 F.

CROSSREFERENCE o RELATED APPLICATIONS or above and also mixtures of suchoils. It should be noted, in this respect, that the term distillate oilsis not T i apphcatlon is dlvision of our copendlng P intended to berestricted to straight-run disillate factions. phca'tlon filed June 1969and now These distillate oils can be straight-run distillate oils,Patent catalytically or thermally cracked (including hydro- BACKGROUNDOF THE IN ENTI cracked) distillate oils, or mixtures of straight-rundistillate oils, naphthas and the like, with cracked distillate (1)Field of the invention 40 stocks and may be of varying viscosities andpour points.

This invention relates to lubricant om o ition nd, Moreover, such oilscan be treated in accordance with in one of its aspects, relates moreparticularly to lubricant Well-known commercial methods, such as a orcaustic compositions which are thermally and oxidatively stabletreatment, hydrogenation, Solvent-refining, y treatment and exhibitreduced tendency to deterioration. Still more and the likeparticularly,in this aspect, the invention relates to such As Previously indicated,the aforementioned Substituted lubricant compositions as lubricant oilsand greases, and indans y also be incorporated, as blending agents inalso to other forms of organi medi i hi h th lubricant vehicles ofgrease compositions. Such greases, bricants can be employed as blendingstocks to modify may comprise a combination of a wide variety oflubricattheir properties, for example such organic media as autoingVehicles and thickening of gelling agents- Thus, greases mati tran i ionfluid hydraulic fl id h p h 5 in which the aforementioned substitutedindans are parifluids, and the like, in which the aforementionedstaticulnltly ettectlve as Vehicle blending agents y bility againstthermal and oxidative deterioration is an P y of the Conventionalhydrocarbon oils of lubricatimportant requisite. ing viscosity, as theoil vehicle, and may include mineral oils or mineral oils in combinationwith synthetic lubricat- 5 ing oils, aliphatic phosphates, esters anddi-desters, sili- This invention relates to lubricant compositions, and,cates, SiloXanes and xa kyl o s d esters. Mi eral stability in lubricantcompositions, for example in such lu ri ating ils, preferably employedas the lubricating representative areas as hydrocarbon lubricant oilsand Vehicle, y be of y Suitable lubricating Viscosity range greases, orin any of the other aforementioned areas, is from about 45 SSU at toabout 6,000 SSU at well known. Prior to the present invention, variouslubri- P y, from nbout to about 250 (2) Description of the prior artcants or lubricant additives have been suggested for such SSU at TheseOils may have viscosity indexes purpose but have not been found toprovide the desired Varying from below 0 to a t 100 or higher. Viscositydegree f improvement I some aspects i h or both, indexes from about 70to about 95 are preferred. The oxidative stability and thermal stabilityhave not been average molecular Weights of these oils y range from igifi tl i d i h f ti d comPosiabout 250 to about 800. The lubricating oilis employed tions. In other instances, lubricants or lubricant addi- 1ntl1e grease Composition in an amount snthoient to tives employed fo Suchpurpose have proved to be costly, stitute the balance of the totalgrease composition, after f outweighing the degree f improvementobtained accounting for the desired quantity of the thickening agent,and other additive components to be included in SUMMARY OF THE INVENTIONthe grease formulation.

In accordance with the present invention, as more As previouslyindicated, the oil vehicles employed in fully hereinafter described,improved lubricants are prothe novel grease formulations of the presentinvention,

porated as blending agents, may comprise mineral oils or combinations ofmineral oils with synthetic oils of lubricating viscosity. When hightemperature stability is not a requirement of the finished grease,mineral oils having a viscosity of at least 40 SSU at 100 F., andparticularly those falling within the range from about 60 SSU to about6,000 SSU at 100 F. may be employed. In in stances, where syntheticvehicles are employed in addition to mineral oils, as the lubricatingvehicle, various compounds of this type may be successfully utilized.Typical synthetic vehicles include: polypropylene, polypropylene glycol,trimethylol propane esters, neopentyl and pentaerythritol esters,di-(2-ethyl hexyl) sebacate, di- (2-ethyl hexyl) adipate, di-butylphthalate, fluorocarbons, silicate esters, silanes, esters ofphosphorus-containing acids, liquid ureas, ferrocene derivatives,hydrogenated mineral oils, chain-type polyphenyls, siloxanes andsilicones (poly-siloxanes), alkyl-substituted diphenyl ethers typifiedby a butyl-substituted bis (p-phenoxy phenyl) ether, phenoxy phenylethers,'etc.

The lubricating vehicles of the aforementioned improved greases of thepresent invention containing the above-described substituted indans asblending agents, are combined with a grease-forming quantity of athickening agent. For this purpose, a wide variety of materials may beemployed. These thickening or gelling agents may include any of theconventional metal salts or soaps, which are dispersed in thelubricating vehicle in grease-forming quantities, in such degree as toimpart to the resulting grease composition, the desired consistency.Other thickening agents that may be employed in the grease formation maycomprise the non-soap thickeners, such as surface-modified clays andsilicas, aryl ureas, calcium complexes and similar materials. Ingeneral, grease thickeners may be employed which do not melt anddissolve when used at the required temperature within a particularenvironment; however, in all other respects, any materials which arenormally employed for thickening or gelling hydrocarbon fluids forforming greases, can be used in preparing the aforementioned improvedgreases in accordance with the present invention.

The substituted indans of the present invention may be prepared, ingeneral, by subjecting a mixture of an isopropyl aromatic compound and ahalogen to a temperature sufficiently high to effect halogenation of theisopropyl group. Thereafter the halogenated isopropyl aromatic compoundthus produced is subjected to elevated temperature, in the presence ofan acidic catalyst, to an extent at which the halogenated isopropylaromatic compound is converted to its corresponding substituted indan.In a preferred embodiment, the aforementioned halogenation is carriedout at about room temperature, or below, but not lower than about C. Apreferred halogenation temperature range is from about 0 C. to about 10C.

As previously indicated, the halogenated isopropyl aromatic compound issubjected to an elevated temperature at which this compound is convertedto its corresponding substituted indan. In a preferred embodiment thehalogenated isopropyl aromatic compound is subjected to an elevatedtemperature within the range from above the halogenation temperatureemployed, but not higher than the boiling point of the halogenatedisopropyl aromatic compound. Preferably the halogenated isopropylaromatic compound, for most purposes, is subjected to a temperature fromabout 100 C. to about 200 C. at which the corresponding substitutedindan is produced.

As hereinbefore indicated, the halogenated isopropyl aromatic compoundis subjected to elevated temperature, in the presence of an acidiccatalyst, for conversion to the corresponding substituted indan. Forthis purpose any acidic material that has an ionization constant greaterthan about 1X10- may be employed, and, exemplary thereof, are catalystscomprising a crystalline aluminosilicate zeolite catalyst in anamorphous silica-alumina matrix; sulfuric acid, trichloroacetic acid;monochloroacetic acid on the aforementioned alumino-silicate zeolitecatalyst, phosphoric acid, nitric acid and other organic and inorganicacids having the aforementioned ionization constant.

DESCRIPTION OF SPECIFIC EMBODIMENTS The following examples will serve toillustrate the novel substituted indans of the present invention, themethod for their preparation and their utility in organic lubricatingmedia.

EXAMPLE 1 Dimers of monoisopropylbiphenyl To a stirred pot containing392 grams (2.0 moles) of monoisopropylbiphenyl and 1176 grams (15.1moles) of benzene at a temperature between about 0 C. and about 10 C.was added dropwise 324 grams (2.03 moles) of bromine. A light source,comprising a -watt clear light bulb, was placed alongside the pot. After10 hours, HBr evolution ceased, indicating completion of the reaction.The benzene was distilled off at reduced pressure leaving a quantitativeyield of 551 grams of product. Upon ananlysis it was found that themolecular weight of the product was 275 (275 calculated) and the brominecontent was 27.6% (29.1% calculated).

The dimerization reaction was performed, employing 280 grams (1.0 mole)of the above-described brominated product with 2.8 grams (1% by weight)of a crushed crystalline aluminosilicate zeolite catalyst in anamorphous silica-alumina matrix at C. in a stirred flask for a period of40 hours. The reaction was considered complete when successive samplesshowed no change by gas chromatographic analysis. The product (209.2grams) was filtered in order to remove the catalyst and Was dissolved inbenzene. After washing the benzene solution to neutrality with water,the benzene was removed and the product was fractionally distilled underreduced pressure. Gas chromatography showed the product mixture tocomprise 25%, by weight, of monoisopropylbiphenyl, 55-60% of the fourexpected isomeric dimers and 15-20% of polymer. Four isomeric dimerswere the result of a diisomeric monoisopropylbiphenyl charge stock. Thechemical and physical properties obtained are hereinafter disclosed inTable I. The substituted indan, thus produced, can be depicted as havingthe structure:

EXAMPLE 2 Codimers of monoisopropylbiphenyl and alpha-methyl styrene 280grams 1.0 mole) of the brominated monoisopropylbiphenyl from Example 1was reacted wtih 118 grams 1.0 mole) of alpha-methyl styrene in thepresence of 8.0 grams (2% by weight) of the acidic clay catalyst ofExample 1 at a temperature of about 150 C. in a stirred flask. After 47hours, 331.8 grams (312 grams calculated) of the resulting product wasrecovered, in the manner described in Example 1. Gas chromatographyshowed unreacted monoisopropylbiphenyl (approximately 15% by weight),alpha-methyl styrene (approximately 24% by weight), the four expectedcodimers (approximately 37% by weight), and the four expected dimers ofmonoisopropylbiphenyl (approximately 24% 'by weight). The productmixture was then fractionally distilled at reduced pressure. Thechemical and physical properties obtained are hereinafter disclosed inTable I. The substituted indan thus produced can be depicted as havingthe structure:

EXAMPLE 3 Dimers of cumylphenylether (phenoxy-cumene) 212 grams (1.0mole) of cumylphenylether in 590 grams (7.6 moles) of benzene wasbrominated with 160 grams (1.0 mole) of bromine in the manner describedin Example 1. The brominated product, following benzene removal,amounted to 308 grams (291 calculated) and had a molecular weight of 296(291 calculated) and a bromine content of 26.2% (27.5% calculated).Dimerization of this material was carried out employing 154 grams (0.53mole) of the brominated material and 4.6 grams (3%) of the acidic claycatalyst of Example 1 at a temperature of about 150 C. for a period of16 hours.

The resulting product was filtered and washed to neu- EXAMPLE 4Monophenoxy-l,1,3-trimethyl-3-phenyl indans By following the procedureand the conditions of Example 3, 0.5 mole of cumylphenylether and 0.5mole of cumene are brominated with 1.0 mole of bromine. The resultingproduct is found to comprise a mixture of1,1,3-trimethyl-3(phenoxy)phenyl indan andphenoxy-l,1,3-trimcthyl-3-phenyl indan. The chemical and physicalproperties of these compounds are hereinafter 6 disclosed in Table I.The substituted indans thus produced can be depicted as having thefollowing structures:

and

EXAMPLE 5 Codimer of thiophenoxycumene and cumene Calculated FoundMolecular weight 344 344 Carbon, percent. 83.72 82. 11 Hydrogen, percent6. 98 6.76 Oxygen, percent 0 0.56 Sulfur, percent 9. 30 9.

The chemical and physical properties are hereinafter disclosed in TableI. The substituted indan thus produced can be depicted as having thestructure:

TABLE I Example 1 2 3 4 6 Molecular weight 38 312 42 328 344 Brominecontent, percent. 0.42 1.19 (0.19) (0.15) 1 Chlorine content, percent 00 0 0 l 0 Bromine number- 0 0.6 I 0 0 0 TAN 0 0 0 0 4 0 Flash F- 515 435490 425 460 Fire, F... 580 610 585 465 515 Pour, F +120 +65 +60 +45 +45KV 100 Solid 3, 806 19, 571 400. 9 468. 9 KV 210 F. 130 14. 68 28. 66 9.9. 86 KV 400 F. 1.55 1.40 AIT, F 830 810 875 870 830 Thermal stability,786 17., 90 min.:

Percent loss 0.007 0.003 0.086 0. 010 0. 13 10 4,020 454.3 210 131. 514. 94 28. 40 8. 40 9. 79 TAN 0. 08 0.31 0. 49 0. 04 Oxy en/corrosion,450 F.:

AKV percent, 100 F 18. 3 AKV percent, 210 F 2,900 184 4. 3 6.0 TAN 2.13.7 0 22 0.44 0 Trace 0 0 0 0 -1. 0 0. 1 0. 1 4. 1 0. 2 0. 4 Trace --0.5 0 5. 1 0 0 0 Br e 0 Oxygen corrosion 450 F., no metals:

AKV percent, 100 F 20. 7 AKV percent, 210 F 6.1 TA 3. 3 0. 51 0 0 1Suliur 9.2%. I crystallized in pure form after several days.

From the foregoing data and examples, 1t will be ap- 3O 2. A process forproduclng an lndane which compnses parent that the novel substitutedindans of the present invention possess chemical and physicalcharacteristics which make them particularly adaptable for use aslubricants, per se, or as blending materials having a wide variety oflubricant compositions for imparting thermal and oxidative stability.Although the present invention has been described herein by means ofcertain specific embodiments and illustrate examples, it is not intendedthat the scope thereof be limited in any way, and is capable of variousmodifications and adaptations, as those skilled in the art will readilyappreciate.

We claim:

1. A substituted indan having the structure and selected from the groupconsisting of 0 and References Cited UNITED STATES PATENTS 2,444,2336/1948 Soday 260-612 X OTHER REFERENCES Elseviers Encyclopedia of Org.Chem., 'vol. 12A (1948), p. 117.

BERNARD HELFIN, Primary Examiner US. Cl. X.R.

260613 R, 515 R, 515 P, 668 R, 668 F, 609 R

